CN102844342B - Especially the vinyl cyanide-silazane multipolymer, Its Preparation Method And Use of fibre shape - Google Patents
Especially the vinyl cyanide-silazane multipolymer, Its Preparation Method And Use of fibre shape Download PDFInfo
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- CN102844342B CN102844342B CN201080056191.3A CN201080056191A CN102844342B CN 102844342 B CN102844342 B CN 102844342B CN 201080056191 A CN201080056191 A CN 201080056191A CN 102844342 B CN102844342 B CN 102844342B
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- silazane
- multipolymer
- vinyl cyanide
- fiber
- mixture
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- 239000000835 fiber Substances 0.000 title claims abstract description 42
- 229920002554 vinyl polymer Polymers 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title description 9
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 title description 8
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000203 mixture Substances 0.000 claims abstract description 24
- 238000000197 pyrolysis Methods 0.000 claims abstract description 14
- 239000000919 ceramic Substances 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 claims abstract description 11
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims description 17
- 125000000217 alkyl group Chemical group 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 238000006116 polymerization reaction Methods 0.000 claims description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- 239000007789 gas Substances 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 6
- 125000001118 alkylidene group Chemical group 0.000 claims description 6
- 239000000945 filler Substances 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 125000005024 alkenyl aryl group Chemical group 0.000 claims description 5
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 5
- 125000005018 aryl alkenyl group Chemical group 0.000 claims description 5
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 5
- 238000010894 electron beam technology Methods 0.000 claims description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 238000010526 radical polymerization reaction Methods 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims 1
- 239000000155 melt Substances 0.000 claims 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 claims 1
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 30
- -1 ammonium halide salt Chemical class 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 229920001709 polysilazane Polymers 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229910052581 Si3N4 Inorganic materials 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 5
- 229910010271 silicon carbide Inorganic materials 0.000 description 5
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910000077 silane Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 229910007991 Si-N Inorganic materials 0.000 description 3
- 229910006294 Si—N Inorganic materials 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 238000005915 ammonolysis reaction Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000004202 carbamide Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 150000004678 hydrides Chemical class 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- WKWOFMSUGVVZIV-UHFFFAOYSA-N n-bis(ethenyl)silyl-n-trimethylsilylmethanamine Chemical compound C[Si](C)(C)N(C)[SiH](C=C)C=C WKWOFMSUGVVZIV-UHFFFAOYSA-N 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- HZBAVWLZSLOCFR-UHFFFAOYSA-N oxosilane Chemical compound [SiH2]=O HZBAVWLZSLOCFR-UHFFFAOYSA-N 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920005594 polymer fiber Polymers 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000001718 carbodiimides Chemical class 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- WQJONRMBVKFKOB-UHFFFAOYSA-N cyanatosulfanyl cyanate Chemical compound N#COSOC#N WQJONRMBVKFKOB-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229920006240 drawn fiber Polymers 0.000 description 1
- 238000000578 dry spinning Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- CCGKOQOJPYTBIH-UHFFFAOYSA-N ethenone Chemical compound C=C=O CCGKOQOJPYTBIH-UHFFFAOYSA-N 0.000 description 1
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000006459 hydrosilylation reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- VIKNJXKGJWUCNN-XGXHKTLJSA-N norethisterone Chemical compound O=C1CC[C@@H]2[C@H]3CC[C@](C)([C@](CC4)(O)C#C)[C@@H]4[C@@H]3CCC2=C1 VIKNJXKGJWUCNN-XGXHKTLJSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000548 poly(silane) polymer Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000003351 stiffener Substances 0.000 description 1
- 125000005504 styryl group Chemical group 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 125000005323 thioketone group Chemical group 0.000 description 1
- RUELTTOHQODFPA-UHFFFAOYSA-N toluene 2,6-diisocyanate Chemical group CC1=C(N=C=O)C=CC=C1N=C=O RUELTTOHQODFPA-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62227—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres
- C04B35/62272—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres based on non-oxide ceramics
- C04B35/62277—Fibres based on carbides
- C04B35/62281—Fibres based on carbides based on silicon carbide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/42—Nitriles
- C08F220/44—Acrylonitrile
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/62227—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres
- C04B35/62272—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining fibres based on non-oxide ceramics
- C04B35/62286—Fibres based on nitrides
- C04B35/62295—Fibres based on nitrides based on silicon nitride
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- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
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- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/626—Preparing or treating the powders individually or as batches ; preparing or treating macroscopic reinforcing agents for ceramic products, e.g. fibres; mechanical aspects section B
- C04B35/628—Coating the powders or the macroscopic reinforcing agents
- C04B35/62802—Powder coating materials
- C04B35/62805—Oxide ceramics
- C04B35/6281—Alkaline earth metal oxides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/60—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule in which all the silicon atoms are connected by linkages other than oxygen atoms
- C08G77/62—Nitrogen atoms
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D01F6/38—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising unsaturated nitriles as the major constituent
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/30—Constituents and secondary phases not being of a fibrous nature
- C04B2235/48—Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
- C04B2235/483—Si-containing organic compounds, e.g. silicone resins, (poly)silanes, (poly)siloxanes or (poly)silazanes
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/52—Constituents or additives characterised by their shapes
- C04B2235/5208—Fibers
- C04B2235/5264—Fibers characterised by the diameter of the fibers
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- C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
- C04B2235/60—Aspects relating to the preparation, properties or mechanical treatment of green bodies or pre-forms
- C04B2235/602—Making the green bodies or pre-forms by moulding
- C04B2235/6021—Extrusion moulding
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- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Ceramic Engineering (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
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- Structural Engineering (AREA)
- Inorganic Chemistry (AREA)
- Nanotechnology (AREA)
- Textile Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Silicon Polymers (AREA)
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- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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- Macromonomer-Based Addition Polymer (AREA)
Abstract
The present invention relates to multipolymer, it obtains by vinyl cyanide or by the reaction with silazane that is at least one monomer, oligomeric and/or that be polymerized of vinyl cyanide and the mixture that can form with the organic molecule of copolymerization of acrylonitrile, and wherein said silazane comprises at least one vinyl double bond.Described multipolymer can transform into fibre shape and/or become not fusible.Fibrous multipolymer is utilized to manufacture ceramic fiber by pyrolysis.
Description
Technical field
The present invention relates to the multipolymer be made up of vinyl cyanide and silazane, described silazane has the double-strand of at least one organic polymerizable, particularly vinyl.This multipolymer consists of fire-retardant material or the raw material of the pyrolysis systems of SiCN (carbonitride of silicium), SiC (silicon carbide) or SiN (silicon nitride) because its silicon atom content, nitrogen atom content and carbon content are such as suitable as.Be no matter the mode of pyrolysis or non-pyrolytic, described material can form arbitrarily, particularly exists with the form of fiber.
Background technology
Above-mentioned system is suitable as the material of broad Application Areas, because it at high temperature has high physical strength and good oxidation-resistance.Pyrolysis product has the characteristic of pottery, and is such as used as the fastening element that should tolerate or resist in the part of high temperature and/or corrosive medium with the form of fiber or ceramic matrix.
At US4,929,704, US5,001,090 and US5,021, describe the addition polymer of the polysilazane comprising isocyanic ester or lsothiocyanates in 533.Utilize different (sulphur) cyanate to produce and be mainly linear product mixtures, wherein-N-C (A)-Ji (A=O or S) introduces in Si-N key.The reaction of the liquid polysilazane reacted with 2,6-tolylene diisocyanate forms the glass product that carbon content significantly improves.Also address following possibility in this article, polysilazane and ketene, thioketones, carbodiimide or CS
2reaction.But do not provide its concrete example or spawn characteristic.Suggestion is using the raw material of this product as the ceramic fiber containing silicon nitride.
Usually by silane/polysilane, SiC-ceramic fiber is synthesized.But this route of synthesis is not that milli is with no difficulty.Therefore, be necessary for the pyrolysis product that the dry spinning process seldom used finds raw material, it is solvable on the one hand, can not melt under the effect of the heat energy but imported when pyrolysis on the other hand.But, usually only have and just can make by loaded down with trivial details approach the material meeting this standard, or must harden before real pyrolysis.TUBergakademieFreiberg can be quoted for this reason and be positioned at the academic paper of Institutf ü rSilicatforschungderFraunhofer-Gesellschaft of W ü rzburg.
Melt-spinning process is used more at large.But, special disadvantageously at this, polymer fiber must be hardened by electron beam irradiation, thus need the high dosage being about 20MGy.
Summary of the invention
In view of this, the object of the invention is to, find a kind of material being applicable to fire prevention and anti-flaming field, it can be processed to stable formed body, such as self-bearing type fiber.In preferred embodiments, the form of fiber that especially can be stable carries out pyrolysis, thus obtains the material consisting of SiC, SiN or SiCN.
In this object solution, provide a kind of by (i) vinyl cyanide or by vinyl cyanide and the mixture that can form with the organic molecule of copolymerization of acrylonitrile, and the multipolymer that (ii) polysilazane material of comprising C=C double bond is made.
Term " silazane " ordinary representation comprises R
1r
2r
3si-N (R
4) SiR
5r
6r
7the compound of group.The very simple representative species of one of this group is disilazane H
3si-NH-SiH
3.Ring-type and linear silazane comprise or by structural unit-Si (R
1r
2)-N (R
3)-composition.By this basic structure, derive many kinds of silazane, its substituting group on silicon can be such as alkyl, thiazolinyl or aryl than hydrogen, and its substituting group on nitrogen can be alkyl or aryl than hydrogen.By introducing extra group as urea groups and different rings and multiple ring, form structure that is oligomeric or polymerization.
Present inventor can determine astoundingly, have one or more C=C double bond silazane can with vinyl cyanide in the solvent being suitable for this material when there is common polyaddition reaction catalyzer copolymerization be polymkeric substance, described polymkeric substance is dissolved in reaction solvent (such as DMF or another kind are suitable for the solvent of vinyl cyanide) used usually.This multipolymer may be dissolved in identical solvent usually, as vinyl cyanide and polyacrylonitrile.After isolating solvent, it at room temperature in solid-state, but when temperature raises is the liquid state of high viscosity.Melt has viscoelastic property, and therefore can stretch becomes fiber.It can utilize electron beam to be cross-linked further after cooling and the optional stretching implemented, and becomes not fusible thus or be converted into the state of rigid plastics.Then the pyrolysis of fiber can be carried out after the after hardening of this fiber.
Co-polymerization is carried out as follows:
Wherein,
X=alkylidene group,
O=0 or 1;
M=0,1,2,3 or arbitrarily larger number;
N=0,1,2,3 or arbitrarily larger number;
P=0,1,2,3 or arbitrarily larger number;
Its condition is: equal 0 when m with p is different, and equals 0 when n with p is different,
The quantity of y=Si-N unit in silazane used,
Substituting group in R=silazane used, corresponds to the R of following formula (I) to (III) usually
2.
Above formula reflects, according to raw material used and polyreaction time length/kind of its temperature/selected catalyzer, the equal length of oligopolymer or the block (p=0) of unequal length of vinyl cyanide and silazane used is contained in formed polymkeric substance, the vinyl cyanide molecule be alternately polymerized and the rotation of silazane molecule be (m and n difference=0) alternately, or (m is not equal to 0 to produce the mixed style with heterogeneity be made up of above-mentioned two kinds of forms, n is not equal to 0, p and is not equal to 0).The suitable reaction pairing material of vinyl cyanide is all monomers, oligomeric or polymerization, the silazane with the thiazolinyl of one or more bond on silicon." oligomeric silazane " should be understood to the silazane with 2 to 10 Siliciumatoms according to the present invention.The silazane of polymerization then refers to the silazane with at least 11 Siliciumatoms.
Spendable silazane or oligomer silazanes/polysilazane have general formula (I)
Or general formula (II)
Or general formula (III)
Wherein,
R
2represent thiazolinyl,
R
3alkyl that represent hydrogen or straight chain, side chain or ring-type, that be substituted or be preferably unsubstituted and R
2identical thiazolinyl or different thiazolinyls, aryl, arylalkyl, alkylaryl, alkenyl aryl or aryl alkenyl, each substituent R when m and/or o wherein in different units is greater than 1
2and R
3different definition can be had, but preferably there is identical definition;
(a) R
2' and R
3' be identical or different, and represent straight chain, side chain or ring-type, the alkyl, thiazolinyl, aryl, arylalkyl, alkylaryl, alkenyl aryl or the aryl alkenyl that are substituted or are preferably unsubstituted, each substituent R when n and/or o wherein in different units is greater than 1
2' and R
3' different definition can be had, but preferably there is identical definition;
Or
(b) R
2and R
2' there is above-mentioned definition, and at least one radicals R of existence
3with at least one radicals R
3' when, the radicals R of all or part
3and radicals R
3' can common designation be unsubstituted or be substituted, straight or branched, the alkylidene group with preferably 2 bridging carbon atoms, the wherein radicals R of optional remainder
3and radicals R
3' there is the definition described in (a); Wherein,
R
4and R
4' represent alkyl, phenyl or the hydrogen with preferably 1 to 4 carbon atom, the multiple radicals R wherein in a silazane molecule
4and/or R
4' can be identical or different;
R
1and R
5can be identical or different, and can have and R
2or R
3identical definition, wherein
R
5si (R can also be represented
1) (R
2') (R
3'), or R
1and R
5common designation singly-bound;
R
6represent Si (R
2) (R
2')-X-R
7-Si (R
2)
q(OR
2')
3-q, wherein X represents O or NR
4,
R
7represent singly-bound or be substituted or be preferably unsubstituted, the alkylidene group of straight chain, side chain or ring-type, q can be 0,1,2 or 3;
P representative has the alkylidene group of 1 to 12 carbon atom, is preferably ethylidene;
M and p represents 1,2,3,4,5,6,7,8,9,10 or integer between 11 and 25000 independently of one another, the integer preferably between 11 and 200; And
N and o represents 0,1,2,3,4,5,6,7,8,9,10 or integer between 11 and 25000 independently of one another, the integer preferably between 11 and 200,
Wherein, blocked ground and optional alternative expression distribute the unit in square brackets equably in each molecule preferably randomly, in other cases.
To formula (I) to the term " unit " that the definition of the silazane of (III) is relevant refer to each in square brackets, there is coefficient (m, n of providing this unit quantity in the molecule ...) molecular moiety.
In the first preferred embodiment, formula (I) is to the R in (III)
2for vinyl.
In this embodiment, R
3be more preferably alkyl, be especially preferably methyl or ethyl.
If the n in formula I to III is at least 1, then relative to first, preferred embodiment independently, preferably selects the substituting group (R of bond on each Siliciumatom of corresponding units as follows
2' and R
3'): alkyl and hydrogen atom, another alkyl, thiazolinyl preferred vinyl or phenyl combine.
In independently the 3rd preferred embodiment, formula (I) has 1 to 6 carbon atom to the alkyl or alkenyl in (III).Be particularly preferably methyl, ethyl and vinyl.Aryl, arylalkyl, alkylaryl, alkenyl aryl or aryl alkenyl preferably have 5 to 12 carbon atoms.Be particularly preferably phenyl and styryl.This embodiment particularly preferably combines with the first embodiment.
At another of formula (I) to (III) independently in preferred embodiment, R
4and/or R
4' represent alkyl, particularly methyl.The carbon fiber utilizing this material to make should have better characteristic.
In independently the 5th preferred embodiment, R
2, R
3, R
2' and R
3' being preferably selected from alkyl, it especially has 1 to 8 carbon atom.
In independently the 6th preferred embodiment, substituent R
2, R
3, R
2' and R
3' with fluorine atom.This embodiment particularly preferably combines with the 4th embodiment.
At another of formula (I) independently in preferred embodiment, coefficient o equals 0.
At another of formula (I) or (II) independently in preferred embodiment, Coefficient m is equal to 0.
In another independently preferred embodiment, R
1and R
5common formation singly-bound.This embodiment is particularly preferred for the compound of formula (I), and wherein coefficient o equals 0, and Coefficient m optionally also equals 0.
In another independently preferred embodiment, o equals 0, m and n is greater than 1, preferably between 2 and 25000, more preferably between 2 and 200.At this, m and n can be equal or not etc.Extraly or alternatively, m and n unit can distribute randomly or equably.At this, they can blocked or the distribution of non-blocked ground.
In another independently preferred embodiment, n and o in formula (I) equals 0, R
5represent Si (R
1) (R
2') (R
3').An example of this embodiment (wherein m=1) is:
Single line in this example especially can represent alkyl, preferably represents methyl, but also can represent hydride, or partly represents alkyl and partly represent hydride.
In another independently preferred embodiment, the m in formula (I) equals 1,2,3,4,5 or integer between 6 and 50, n and o equals 0, or the mixture of this type of different silazane.At this, substituent R
1and R
5can be identical or different, and have and R
3identical definition, wherein R
5also Si (R can be represented
1) (R
2') (R
3').The form that one or more these type of silazane optionally especially can also contain the mixture of silazane exists, wherein R
1and R
5common designation singly-bound.
In another independently preferred embodiment, the o in formula (I) is that 0, m and n is equal or not etc., and represents the numerical value between 2 and 200-25000.At this, substituent R
1and R
5can be identical or different, and have and R
3identical definition, wherein R
5also Si (R can be represented
1) (R
2') (R
3').The form that one or more these type of silazane optionally especially can also contain the mixture of silazane exists, wherein R
1and R
5common designation singly-bound.
Example is following oligomer/polymer:
Wherein, the unit in square brackets with given mutual ratio randomly, optional blocked ground and distributing in the molecule equably in other cases, described molecule comprises the hydrogen atom or alkyl or aryl that are positioned at end.
In another independently preferred embodiment, coefficient n and o is equal to 0, and Coefficient m equals 3, R
1and R
5common designation singly-bound.This embodiment can represent generally by formula (Ia):
Wherein, R
2, R
3and R
4have such as formula the definition described in (I).
At another of formula (I) independently in preferred embodiment, n and o equals the numerical value that 0, m equals 2,3,4,5,6,7,8,9,10 or larger, R
1and R
5common designation singly-bound.
At another of formula (I) and (II) independently in preferred embodiment, m and n equals the numerical value of 2,3,4,5,6,7,8,9,10 or larger separately, R
1and R
5common designation singly-bound.These compounds can exemplarily such as be represented (wherein o or p equals 0) by following formula again:
Wherein, unit in square brackets randomly or blocked ground, can also distribute in the molecule equably in some cases, with m doubly or n doubly or in the end shown in formula when exist with common (m+n) mutual ratio doubly, but this molecule exists with the form of closed chain.The scheme of this change especially can contain the form existence of the mixture of the silazane of corresponding open chain, and for the present invention.
As long as above-mentioned preferred embodiment is not mutually exclusive, just wherein two or more can be combined.
Wherein o equals the silazane of the formula (I) of 0 is commercially available acquisition, and can according to standard method, and particularly the ammonolysis of single halosilanes obtains, such as, at US4,395,460 and wherein quoted document described in.At this, such as pass through the silazane of the reacting generating (I) of single halosilanes and three organic groups, wherein coefficient n and o equals 0, and Coefficient m equals 1, R
5represent Si (R
1) (R
2') (R
3').Described organic group is not eliminated in the reaction.
Equally can with the document US6 of Kion company, 329,487B1 analogously, make single halosilanes, two halosilanes or three halosilanes in liquefied ammonia, carry out ammonia solution in pressure assembly, thus obtain the silazane of general formula (I).
If the halosilanes having at least one Si-H key at this reacts individually and/or together with two halosilanes or three halosilanes in excessive anhydrous liquid ammonia, and keep in the medium with the longer time, then passing through produced ammonium halide salt or corresponding acid along with the time forms polymerisate by reacting away Si-H key in the environment of souring, wherein Coefficient m, n and o have than numerical value higher described in before and/or different ratios, dissolve and Ionized ammonium halide and carry out catalysis possibly by existing.
US6,329,487B1 are also described and can be obtained corresponding polymerisate by the effect being dissolved in the sodium in ammonia.
US4,621,383 and WO87/05298 also describe possibility by transition metal-catalyzed Reactive Synthesis polysilazane.
By suitably selecting the organic substituent on the Siliciumatom of the mixture of silane or corresponding starting silane, the method can be adopted to produce the silane of many kinds of formulas (I), wherein coefficient o equals 0, wherein usually forms the mixture of linear polymer and chain polymer.
Reaction mechanism is see the Ph D dissertation " Mikrostrukturierung of MichaelSchulz at ForschungszentrumKarlsruhe, Institutf ü rMaterialforschung
polymeremitHilfederUV-und
", in November, 2003, FZKA6901.Also describe the preparation of the silazane of formula (I) at this, wherein coefficient o equals 0, has Siliciumatom in the block of Coefficient m and n with different substituting groups.
At this also see the preparation of urea silazane: if add the isocyanic ester of simple function to silazane, then by forming the reaction (silazane see above-mentioned formula (II)) that urea groups carries out being inserted by NCO base in N-H key.In addition, about the preparation of urea silazane and poly-(urea silazane), see US6,165,551, US4,929,704 and US3,239,489.
US6,652,978B2 disclose the preparation of the compound (silazane that alkoxyl group replaces) of formula (III).In order to prepare this compound, the silazane that can make monomer or oligomeric/polymerization wherein o equals the formula (I) of 0 reacts with organoalkoxysilane such as the 3-aminopropyl-triethoxyl silane containing amino or hydroxyl.
G.Motz (G.Motz, Ph D dissertation,
stuttgart, 1995) Ph D dissertation is the preparation method that example describes a kind of wherein o and is not equal to the compound of the formula (I) of 0 with the ammonolysis of two (dichloromethyl silyl) ethane of 1,2-particularly.According to " the ModifizierungdesABSE-PolycarbosilazansmitMulti-WalledCar bonNanotubeszurHerstellung of S.Kokott and G.Motz
massen ", Mat.-wiss.u.Werkstofftech.2007,38 (11), 894-900, by by MeHSiCl
2and MeViSiCl
2the hydrosilylation of the mixture of composition and ammonolysis realize the preparation of a kind of special representative substances ABSE of this compounds.
By making corresponding halosilanes and alkylamine react, the silazane of N-alkyl-replacement can be prepared to those skilled in the art without any problems in the same manner, as US4,935,481 and US4,595, described in 775.
The amount of substance proportionality principle of silazane used and vinyl cyanide used not critical.Therefore, the molar ratio of silazane and vinyl cyanide such as can in the scope of 100: 1 to 1: 100.The ratio of 4: 1 to 1: 20 is proved to be favourable.The molar ratio of silazane is preferably more than vinyl cyanide.
React in the solvent common for these components.Especially can use for the conventional solvent of the polymerization of vinyl cyanide, as DMF, DOX-2-ketone, N,N-DIMETHYLACETAMIDE or DMSO.Add for the conventional catalyzer of radical polymerization effect, particularly polyaddition.Such as can use for the known catalyzer of the preparation of polyacrylonitrile at this, such as azo isobutyronitrile.
Usually react to (or reflux temperature under) at solvent at 100 DEG C in the temperature such as 40 DEG C improved; Usually terminated after several hours.Obtain the product with linear-C-C-connector.If one or more silazane used comprise at least two thiazolinyls, then this molecule from a silazane molecule or can be included by this type of connector multiple.Therefore according to spatial depiction, this silazane can be the starting point of three-dimensional connector.If use silazane that is oligomeric or that be polymerized completely, then corresponding product also comprises the chain or ring that are made up of Si-N base, which further improves the density of this structure.
Preferably only form material according to the invention by vinyl cyanide and silazane.But it also can contain other additives.
Such as can consider can with the organic substance of copolymerization of acrylonitrile (monomer or other organic molecules) as additive.For this reason, vinylbenzene and/or divinyl and/or vinylcarbazole can such as be considered.In order to too seriously damage desired characteristic especially fire line and anti-flammable, based on the total amount of vinyl cyanide and organic molecule, the content of this additive should be not more than 20 % by weight usually.Preferably one or more organic substances be mixed in this solution or be pre-loaded into wherein, wherein also introducing other components, to be polymerized.
Extraly or alternatively, described material can contain one or more fillers, and it preferably has inorganic nature, but also can be optionally organically-modified, such as, in order to make polymerization transfiguration easy.Based on the weight of this material, the addition of filler as required can up to about 60 % by weight.Be preferably up to 20 % by weight.Preferably before isolating solvent, add filler.
In principle, material of the present invention can have arbitrary form.But it is preferred for manufacturing fiber or existing with fibre shape.
In order to manufacture fiber, isolate solvent from the polymers soln of gained (or polymer suspension, if be added with filler).This product is at room temperature normally solid-state.If raised temperature, then produce the viscoelastic melt be made up of mutual hook polymer molecule even.In many cases, softening temperature is higher than 100 DEG C.
Extrude preferably by the injector head with multiple nozzle, by melt, preferred packless melt drawn fiber.Nozzle cross-section is preferably about 150 to 400 μm.Make fiber cool subsequently, preferably stretch at this, wherein diameter becomes obviously less; Preferably be wound around when manufacturing fiber continuously.
The fiber of acquisition like this is suitable for being processed into textile material, such as, interweave, knit, plain weave, or introduces in polymeric matrix as stiffener.It is in particular for fire protection field, has only fiery characteristic because its content due to silicon and nitrogen is high.
In addition, by pyrolysis, this fiber can be transformed into ceramic fiber.For this reason, first passage common method, such as, by electron beam irradiation, makes the polymer fiber obtained by melt become not fusible.The dosage be about in the scope of 200KGy is enough usually to this.
Preferably in the shielding gas such as argon gas of anaerobic, carry out pyrolysis.Can selective reaction condition (gas atmosphere, temperature), the ratio of silicon and nitrogen and carbon in product is kept almost constant (but carbon content slightly reduces usually, because can form a small amount of methane).SiCN ceramic fiber can be obtained in this way.Optionally by known measure, such as, by fiber is warmed at least 1450 DEG C, wherein can generate SiC, or by carrying out pyrolysis in ammonia atmosphere, generate methane by carbon, thus converting it into as SiC fiber or SiN fiber.
Embodiment
Following examples should set forth the present invention in more detail.The equal weight proportions provided refers to double bond (vinyl or acryl).
Embodiment 1
Divinyl tetramethyl-disilazane (DVTMDS) and vinyl cyanide (ACN) react with the ratio of 1: 1
In nitrogen atmosphere, 1.59 grams of (8.6 moles) DVTMDS, 0.91 gram of (17.2mmol) ACN and 2.5 gram dimethyl formamide (DMF) loading are equipped with in the three-necked flask of reflux cooling device, gas feed pipe and the magnetic stirring apparatus with bubble counter.37.5mg azo isobutyronitrile (AIBN) is added this mixture, stirs 5 hours at 75 DEG C subsequently.According to batch acquisition from dark yellow to amber liquid.According to Raman spectrum, the vinyl double bond almost completely dissolve of silazane.
Embodiment 2
Divinyl tetramethyl-disilazane and vinyl cyanide react with the ratio of 1: 4
In nitrogen atmosphere, 0.76 gram of (4.1 moles) DVTMDS, 1.74 grams of (32.8mmol) ACN and 2.5 gram dimethyl formamide (DMF) loadings are equipped with in the three-necked flask of reflux cooling device, gas feed pipe and the magnetic stirring apparatus with bubble counter.37.5mg azo isobutyronitrile (AIBN) is added this mixture, stirs 5 hours at 75 DEG C subsequently.According to batch acquisition from dark yellow to amber solution.According to Raman spectrum, the vinyl double bond almost completely dissolve of silazane.
Embodiment 3
The cyclic oxosilane obtained by making the mixture ammonia solution be made up of 50 % by mole of Ethylene Dichloride butyldimethylsilyl and 50 % by mole of dichlorodimethylsilane (VML50) and vinyl cyanide react with the mol ratio of 1: 1
In nitrogen atmosphere, 1.82 grams of VML50,0.61 gram of ACN and 2.5 gram dimethyl formamide (DMF) loading are equipped with in the three-necked flask of reflux cooling device, gas feed pipe and the magnetic stirring apparatus with bubble counter.75mg (0.46mmol) azo isobutyronitrile (AIBN) is added this mixture, stirs 5 hours at 75 DEG C subsequently.Obtain more full-bodied yellow solution.
Embodiment 4
The cyclic oxosilane obtained by making the mixture ammonia solution be made up of 50 % by mole of Ethylene Dichloride butyldimethylsilyl and 50 % by mole of dichlorodimethylsilane (VML50) and vinyl cyanide react with the mol ratio of 1: 4
In nitrogen atmosphere, 1.04 grams of (0.66mmol equivalent) VML50,1.39 grams of (26.1mmol) ACN and 2.5 gram dimethyl formamide (DMF) loadings are equipped with in the three-necked flask of reflux cooling device, gas feed pipe and the magnetic stirring apparatus with bubble counter.75mg (0.46mmol) azo isobutyronitrile (AIBN) is added this mixture, stirs 5 hours at 75 DEG C subsequently.After 2 hours, just owing to forming gel, stirring is paused.Obtain yellow gel.
Embodiment 5-manufactures fiber
Remove solvent to by vinyl silazane with the polymkeric substance obtained that is polymerized of vinyl cyanide and heat, until form viscous melt.Be that the nozzle plate of the nozzle of 200 or 300 μm extrudes by it by having hundreds of diameters.The indoor that the line formed has normal room temperature are declined by gravity.Anchoring fiber end, is wrapped on the cylinder of rotation by stretching by fibrous bundle, wherein by the thickness of tensile fiber to about 10 to 30 μm.
The later stage of embodiment 6-fiber is cross-linked
With the fiber of the electron beam irradiation embodiment 5 of 200KGy.It becomes rigid plastics subsequently, and no longer can melt.
Claims (16)
1. multipolymer, is obtained by the reaction of following material:
The mixture of (i) vinyl cyanide or vinyl cyanide and other additives, with
(ii) at least one monomer, silazane that is oligomeric and/or polymerization,
Wherein said silazane comprises at least one vinyl double bond, and is selected from the silazane of the silazane of general formula (I), the silazane of general formula (II) and general formula (III):
Wherein,
(a) R
2represent thiazolinyl,
R
3alkyl that represent hydrogen or straight chain, side chain or ring-type, that be substituted or be unsubstituted and R
2identical thiazolinyl or different thiazolinyls, aryl, arylalkyl, alkylaryl, alkenyl aryl or aryl alkenyl, each substituent R when m and/or o wherein in different units is greater than 1
2and R
3there is similar and different definition;
R
2' and R
3' identical or different, and represent straight chain, side chain or ring-type, the alkyl, thiazolinyl, aryl, arylalkyl, alkylaryl, alkenyl aryl or the aryl alkenyl that are substituted or are unsubstituted, each substituent R when n and/or o wherein in different units is greater than 1
2' and R
3' there is different definition or identical definition;
Or
If there is at least one radicals R in (b)
3and radicals R
3', then R
2and R
2' there is above-mentioned definition, (i) all or (ii) part radicals R
3and R
3alkylidene group that ' common designation is unsubstituted or is substituted, straight or branched, wherein in the radicals R of the middle remainder of situation (ii)
3and R
3' there is the definition provided in (a);
Wherein,
R
4and R
4' represent alkyl, phenyl or hydrogen, the multiple radicals R wherein in each molecule of compound (I) to (III)
4and/or R
4' can be identical or different,
R
1and R
5identical or different, and can have and R
2or R
3identical definition, wherein R
5si (R can also be represented
1) (R
2') (R
3'), or R
1and R
5common designation singly-bound,
R
6represent Si (R
2) (R
2')-X-R
7-Si (R
2)
q(OR
2')
3-q, wherein X represents O or NR
4,
R
7represent singly-bound or be substituted or be unsubstituted, the alkylidene group of straight chain, side chain or ring-type, q can be 0,1,2 or 3,
P representative has the alkylidene group of 1 to 12 carbon atom,
M and p represents 1,2,3,4,5,6,7,8,9,10 or integer between 11 and 25000 independently of one another, and
N and o represents 0,1,2,3,4,5,6,7,8,9,10 or integer between 11 and 25000 independently of one another,
Wherein, the unit in square brackets can equably, randomly or blocked ground distribute in each molecule.
2. multipolymer according to claim 1, it is only obtained by vinyl cyanide and silazane.
3. multipolymer according to claim 1, is obtained by the reaction of following material:
I (), by vinyl cyanide and the mixture that can form with the organic molecule of copolymerization of acrylonitrile, wherein said organic molecule maximum level is in the mixture 20 % by weight; And
(ii) monomer, silazane that is oligomeric and/or polymerization as defined in claim 1, wherein said silazane comprises at least one vinyl double bond.
4. multipolymer according to claim 3, the mixture that wherein said organic molecule is selected from vinylbenzene, divinyl, vinylcarbazole and is made up of the two or all three kinds in these molecules.
5. according to the multipolymer of one of aforementioned claim, it is characterized in that, it is filled with filler.
6., according to the multipolymer of one of Claims 1-4, it is fibre shape.
7. multipolymer according to claim 6, is characterized in that, it is not fusible.
8. multipolymer according to claim 6 is for the manufacture of the purposes of ceramic fiber.
9., for the manufacture of the method for multipolymer as claimed in claim 1, it is characterized in that, will
The mixture of (i) vinyl cyanide or vinyl cyanide and other additives, and
(ii) at least one comprises silazane that the is monomer of at least one vinyl double bond, oligomeric and/or polymerization
Dissolve in a solvent, and carry out copolymerization by the catalyzer for radical polymerization.
10. method according to claim 9, is characterized in that, filler is added described solvent.
11., for the manufacture of the method for the fiber be made up of multipolymer as claimed in claim 1, is characterized in that,
(A) by the mixture of (i) vinyl cyanide or vinyl cyanide and other additives, and
(ii) at least one comprises silazane dissolving that the is monomer of at least one vinyl double bond, oligomeric and/or polymerization in a solvent as defined in claim 1, and carries out copolymerization by the catalyzer for radical polymerization;
(B) solvent is isolated from the copolymer solution of gained;
(C) according to (B) if the product obtained its be not at room temperature liquid or viscosity, just convert it into as melt; And
(D) by the melt that one or more nozzle is extruded described product or produced by it, wherein fiber is formed.
12. methods according to claim 11, the fiber wherein extruded becomes not fusible subsequently.
13. methods according to claim 12, wherein not fusible by making described fiber become with electron beam irradiation.
14., for the manufacture of the method for SiCN ceramic fiber, is characterized in that, make in oxygen-free shielding gas, to carry out pyrolysis according to the not fusible fiber of the method manufacture of claim 12 or 13.
15., for the manufacture of the method for SiC ceramic fiber, is characterized in that, the SiCN ceramic fiber manufactured according to claim 14 is heated at least 1450 DEG C.
16., for the manufacture of the method for SiN ceramic fiber, is characterized in that, make the SiCN ceramic fiber manufactured according to claim 14 carry out pyrolysis in ammonia atmosphere.
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| DE102009059777.8 | 2009-12-09 | ||
| DE102009059777A DE102009059777A1 (en) | 2009-12-09 | 2009-12-09 | Acrylonitrile-silazane copolymers, especially in fiber form, process for their preparation and their use |
| PCT/EP2010/069196 WO2011070081A1 (en) | 2009-12-09 | 2010-12-08 | Acrylonitrile-silazane copolymers, especially in fiber form, process for preparation thereof and use thereof |
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| EP (1) | EP2510024B1 (en) |
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| WO2006071907A1 (en) * | 2004-12-29 | 2006-07-06 | 3M Innovative Properties Company | Multi-photon polymerizable pre-ceramic polymeric compositions |
| WO2006071914A2 (en) * | 2004-12-29 | 2006-07-06 | 3M Innovative Properties Company | Single- and multi-photon polymerizable pre-ceramic polymeric compositions |
| CN101501088A (en) * | 2006-06-06 | 2009-08-05 | 道康宁公司 | A silicone acrylate hybrid composition |
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- 2009-12-09 DE DE102009059777A patent/DE102009059777A1/en not_active Withdrawn
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2010
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- 2010-12-08 JP JP2012542542A patent/JP5636060B2/en not_active Expired - Fee Related
- 2010-12-08 WO PCT/EP2010/069196 patent/WO2011070081A1/en active Application Filing
- 2010-12-08 EP EP10787475.2A patent/EP2510024B1/en not_active Not-in-force
- 2010-12-08 RU RU2012128553/04A patent/RU2012128553A/en not_active Application Discontinuation
- 2010-12-08 US US13/514,795 patent/US9096702B2/en not_active Expired - Fee Related
- 2010-12-08 KR KR1020127017836A patent/KR20130006593A/en not_active Application Discontinuation
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| WO2006071907A1 (en) * | 2004-12-29 | 2006-07-06 | 3M Innovative Properties Company | Multi-photon polymerizable pre-ceramic polymeric compositions |
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| JP5636060B2 (en) | 2014-12-03 |
| WO2011070081A8 (en) | 2012-06-28 |
| WO2011070081A1 (en) | 2011-06-16 |
| EP2510024A1 (en) | 2012-10-17 |
| KR20130006593A (en) | 2013-01-17 |
| JP2013513683A (en) | 2013-04-22 |
| US20120248641A1 (en) | 2012-10-04 |
| DE102009059777A1 (en) | 2011-06-16 |
| US9096702B2 (en) | 2015-08-04 |
| RU2012128553A (en) | 2014-01-20 |
| CN102844342A (en) | 2012-12-26 |
| EP2510024B1 (en) | 2013-10-30 |
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